EP1379470A2 - Oxydes de fer presentant un degre eleve d'affinage - Google Patents

Oxydes de fer presentant un degre eleve d'affinage

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Publication number
EP1379470A2
EP1379470A2 EP02732550A EP02732550A EP1379470A2 EP 1379470 A2 EP1379470 A2 EP 1379470A2 EP 02732550 A EP02732550 A EP 02732550A EP 02732550 A EP02732550 A EP 02732550A EP 1379470 A2 EP1379470 A2 EP 1379470A2
Authority
EP
European Patent Office
Prior art keywords
iron oxide
iron
catalyst
oxides
refining
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02732550A
Other languages
German (de)
English (en)
Other versions
EP1379470B1 (fr
EP1379470B2 (fr
EP1379470B9 (fr
Inventor
Christian Walsdorff
Michael Baier
Reinhard KÖRNER
Klaus Harth
Gerald Vorberg
Wilhelm Ruppel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Priority claimed from DE10117996A external-priority patent/DE10117996A1/de
Priority claimed from DE10154718A external-priority patent/DE10154718A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1379470A2 publication Critical patent/EP1379470A2/fr
Publication of EP1379470B1 publication Critical patent/EP1379470B1/fr
Publication of EP1379470B2 publication Critical patent/EP1379470B2/fr
Application granted granted Critical
Publication of EP1379470B9 publication Critical patent/EP1379470B9/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • C01G49/06Ferric oxide [Fe2O3]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • B01J37/088Decomposition of a metal salt
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333Catalytic processes
    • C07C5/3332Catalytic processes with metal oxides or metal sulfides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/881Molybdenum and iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872Alkali or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/51Particles with a specific particle size distribution
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/14Pore volume
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74Iron group metals
    • C07C2523/745Iron
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00Chemistry of inorganic compounds
    • Y10S423/01Waste acid containing iron

Definitions

  • the present invention relates to a process for refining iron oxide, the iron oxide being calcined at at least 700 ° C.
  • EP-A-1 027 928 describes a catalyst, in particular for the dehydrogenation of ethylbenzene to styrene, which is prepared using an iron oxide obtained by spray roasting an iron salt solution, in particular hydrochloric iron solutions (Ruthner process).
  • the disadvantage of such iron oxides is the high residual chloride content contained therein.
  • iron oxides are known as starting material for catalysts, in particular for the dehydrogenation of ethylbenzene to styrene, which are restructured by mixing with another metal compound and subsequent calcination, and which have very small BET surfaces.
  • the disadvantage of such a restructuring is the contamination of the iron oxide by the added metal compound.
  • JP-A-61-72601 discloses a fluidized bed process for splitting heavy hydrocarbons into lighter ones (catalytic cracking) using a catalyst, the powdered catalyst being obtained by slurrying an iron oxide powder with water, spray drying and finally calcining at temperatures between 1200 and 1600 ° C.
  • a disadvantage of this process is the considerable effort involved in the production and the high calcination temperatures.
  • EP-A-827 488 describes a reduction in the residual chloride content in iron oxides, in particular in iron oxides from the processing of hydrochloric acid pickling solutions, by mixing the iron oxide with a hydrated metal compound and then calcining.
  • the disadvantage of this method is the relatively large outlay in the production.
  • the object of the present invention was therefore to remedy the disadvantages mentioned above.
  • the method according to the invention can be carried out as follows:
  • iron oxide is suitable for refinement in the sense of the present invention 1 ; iron oxides produced by working up hydrochloric acid pickling solutions, such as occur in the steel industry, are particularly suitable, in particular iron oxides produced by spray roasting of hydrochloric acid pickling solutions (Ruthner process).
  • the iron oxide can be preferably pretreated, ie without mechanical pretreatment, preferably dry, ie without prior treatment with water, an acid or base or any other substance of a discontinuous or preferably continuous calcination at a temperature of 700 to 1200 ° C, preferably 840 to 1150 ° C, particularly preferably 850 to 1100 ° C, in particular 860 to 1000 ° C generally for 0.1 to 24 h, preferably 0.25 to 10 h, particularly preferably 0.3 to 5 h, in particular 0 , 5 to 1.5 hours. All known furnaces are suitable for calcination. The calcination can be carried out batchwise, for example in muffle furnaces, or continuously, for example in rotary tube furnaces or in belt calciners.
  • the calcination can be carried out at only one temperature or in stages over different temperatures or via a continuous temperature ramp.
  • tapping devices should be used which prevent the iron oxide from sticking to the wall of the rotary tube and which ensure continuous delivery of the iron oxide.
  • the calcination is advantageously carried out in smooth rotary tubes without internals, whereby the dwell time can be adjusted by the speed of rotation, inlet speed and inclination of the rotary tube.
  • the calcination is also advantageously carried out under a gas stream, for example nitrogen or air, in order to drive off chlorine compounds which are released and expediently to remove them in a downstream exhaust gas scrubber.
  • the chloride content can advantageously be reduced in a resting bed, for example when calcining in a muffle furnace or on a belt calciner.
  • a resting bed for example when calcining in a muffle furnace or on a belt calciner.
  • somewhat lower temperatures may be required to reduce the chloride content than in a bed at rest, which can lead to a comparatively further reduced BET surface area.
  • All iron oxides are suitable as iron oxides for the refinement according to the invention, regardless of their production. Suitable are, for example, natural, preferably technically manufactured and commercially available iron oxides, in particular iron oxides produced by working up hydrochloric acid pickling solutions. These can contain, for example, a residual chloride content and / or compounds of titanium, manganese, aluminum, chromium, phosphorus, zinc, copper, molybdenum, tungsten, silicon, nickel, magnesium, potassium, sodium, cobalt, vanadium, zirconium, niobium, sulfur, Contain lanthanum, lead, tin and / or calcium.
  • iron oxides which are produced by spray rusting of hydrochloric acid pickling solutions in the steel industry and as Fe 2 0 3 with a residual chloride content between 0 and 10000 pp, preferably between 50 and 5000 ppm and particularly preferably between 500 and 2000 ppm, usually in ha etite Crystal structure and a BET surface area of typically 3 to 5 m 2 / g are present.
  • the iron oxides refined according to the invention generally have a residual chloride content of less than 400 ppm, preferably less than 300 ppm and particularly preferably less than 250 ppm, in particular less than 200 ppm.
  • the average particle size, determined by laser diffraction as described below, is generally more than 5 ⁇ m, ie 5.1 to 200 ⁇ m, preferably 8 to 100 ⁇ m, particularly preferably 10 to 80 ⁇ m and very particularly preferably 12 to 30 ⁇ m, and the fine fraction with particle sizes of less than 1 ⁇ m generally less than 15% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight.
  • the BET surface area of the iron oxides 5 treated according to the invention is generally 0.4 to 5 m 2 / g, preferably 0.4 to 3.5 m 2 / g, particularly preferably 0.5 to 3 m 2 / g, and in particular 0.6 to 2.5 m 2 / g, very particularly preferably 0.7 to 2 m 2 / g.
  • the iron oxides treated according to the invention generally have a hematite structure. They can be used for a number of technical applications 10, for example pharmaceuticals, cosmetics, magnetic tape coatings, chemical reactions, catalysts or for the production of catalysts, in particular for the production of catalysts for the dehydrogenation of ethylbenzene to styrene.
  • Ethylbenzene can be made by isothermal or adiabatic processes.
  • temperatures of 450 to 700 ° C., preferably 520 to 650 ° C. in the gas phase with the addition of steam at a pressure of 0.1 to 5 bar, are generally used.
  • adiabatic process is generally carried out at temperatures of 450 to 7 '00 ° C, preferably 520 and 650 ° C in the gas phase with addition of water vapor at a pressure of 0.1 to 2 bar, preferably from 0.2 "to 1 bar , particularly preferred
  • Such catalysts usually hold iron oxide and an alkali metal compound, such as potassium oxide.
  • such catalysts usually contain a number of promoters.
  • promoters For example, compounds of calcium, magnesium, cerium, molybdenum, tungsten, chromium and titanium have been described as promoters.
  • 35 of the catalysts can be used as feedstocks, compounds of the promoters as they are in the finished catalyst, or compounds that convert during the manufacturing process into compounds as they are in the finished catalyst. Auxiliaries can also be added to the starting materials
  • the feed materials can be mixed directly in a mixer, kneader or preferably a mix-muller. You can
  • Preferred strand forms include extrudates of 2 to 10 mm in diameter.
  • the cross section of the extrudates can be round or in other shapes. Extrudates with a rotationally symmetrical cross section, in particular with a diameter of 3 mm, and extrudates with a star-shaped or those with a toothed wheel cross section, in particular with diameters of 4.5 or 6 mm, are particularly preferred.
  • the extrudates can be broken or cut to length by cutting devices.
  • the catalysts can also be shaped by tableting.
  • the catalysts produced according to the invention are distinguished by larger average pore radii and a smaller BET surface area than otherwise analogous, but catalysts produced from iron oxide not refined according to the invention.
  • Catalysts which are produced instead of conventional iron oxide according to the prior art using the iron oxide refined according to the invention show improved activity and selectivity.
  • the proportion of iron oxide pretreated according to the invention in the total iron oxide contained in the catalyst should be at least 30% by weight, preferably at least 60% by weight and very particularly preferably at least 90% by weight.
  • the proportion of iron oxide refined according to the invention in the total iron oxide content is particularly preferably 100% by weight.
  • Catalysts for the dehydrogenation of ethylbenzene to styrene produced using iron oxide refined according to the invention can be used in all processes and process variants. They are particularly suitable for use with steam / ethylbenzene (D / EB) ratios of 0.6 to 2.5 kg / kg.
  • the catalysts produced according to the invention are characterized by a low chloride content of less than 500 ppm, typically less than 300 ppm, particularly preferably less than 200 ppm and an average pore diameter of 0.3 to 3 ⁇ m, typically 0.5 to 1 , 5 ⁇ m.
  • the iron oxide type HP (Hösch Premium) from Thyssen-Krupp was used as the starting material, which is produced by the so-called Ruthner process by spray roasting of hydrochloric iron solutions.
  • the residual chloride content was determined coulometrically in all cases.
  • the particle size of the iron oxide was determined using the Mastersizer S device from Malvern (lens: 300 RFm, measuring range 0.05 up to 880 mm).
  • the module MS17 was used for this. This is a sample container for dispersion in an aqueous medium with a built-in paddle stirrer, integrated ultrasonic generator and circulation pump. Before measurement 5, the integrated ultrasonic bath (setting 100%) was put into operation and after 5 min. Dispersion time the measurement made with the ultrasound running.
  • Specific BET surfaces were determined in accordance with the DIN 66133 specification, pore volumes and mean pore radii were determined in accordance with the DIN 66131 10 specification.
  • the iron oxide was pretreated analogously to Example 6, but kept at 900 ° C. for 2 hours.
  • the iron oxide was continuously calcined in a rotary tube under an air stream.
  • the rotary tube was equipped with three tapping devices.
  • the wall temperature of the rotary tube was 70 ° C, the residence time of the iron oxide was approximately one hour.
  • a catalyst was produced analogously to Example 8, but instead of the refined iron oxide from Example 1, non-refined iron oxide (type HP from Thyssen-Krupp) was used as the starting material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Compounds Of Iron (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

L'invention concerne un procédé d'affinage d'oxydes de fer, selon lequel on soumet à une calcination les oxydes de fer à une température de 700 à 1200 °C.
EP02732550A 2001-04-10 2002-04-03 Oxydes de fer presentant un degre eleve d'affinage Expired - Lifetime EP1379470B9 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10117996 2001-04-10
DE10117996A DE10117996A1 (de) 2001-04-10 2001-04-10 Eisenoxide mit höherem Veredelungsgrad
DE10154718A DE10154718A1 (de) 2001-11-09 2001-11-09 Eisenoxide mit höherem Veredelungsgrad
DE10154718 2001-11-09
PCT/EP2002/003672 WO2002083569A2 (fr) 2001-04-10 2002-04-03 Oxydes de fer presentant un degre eleve d'affinage

Publications (4)

Publication Number Publication Date
EP1379470A2 true EP1379470A2 (fr) 2004-01-14
EP1379470B1 EP1379470B1 (fr) 2007-06-27
EP1379470B2 EP1379470B2 (fr) 2012-03-14
EP1379470B9 EP1379470B9 (fr) 2012-05-02

Family

ID=26009063

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02732550A Expired - Lifetime EP1379470B9 (fr) 2001-04-10 2002-04-03 Oxydes de fer presentant un degre eleve d'affinage

Country Status (10)

Country Link
US (1) US7186395B2 (fr)
EP (1) EP1379470B9 (fr)
JP (1) JP4383055B2 (fr)
KR (1) KR20030092062A (fr)
CN (1) CN1215984C (fr)
AT (1) ATE365702T1 (fr)
AU (1) AU2002304805A1 (fr)
DE (1) DE50210381D1 (fr)
DK (1) DK1379470T3 (fr)
WO (1) WO2002083569A2 (fr)

Cited By (1)

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US8003837B2 (en) 2005-07-22 2011-08-23 Basf Se Catalysts for dehydrogenation and/or hydrogenation of hydrocarbons, processes for preparing the same, and uses therefor

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DE102005058416A1 (de) * 2005-12-07 2007-06-14 Basf Ag Verbesserter Katalysator und Verfahren zur Polymerisation cyclischer Ether
ATE495138T1 (de) * 2006-12-01 2011-01-15 Michael J Ruthner Verfahren zur herstellung von eisenpulver oder stahlpulver aus eisenoxid-pulver durch oxidation und reduktion
CA2674950A1 (fr) * 2007-01-18 2008-07-24 Shell Internationale Research Maatschappij B.V. Catalyseur, elaboration et utilisation
AR065023A1 (es) * 2007-01-30 2009-05-13 Shell Int Research Un catalizador de deshidrogenacion, su proceso de preparacion y su metodo de uso
EP2152412A2 (fr) * 2007-05-03 2010-02-17 Shell Internationale Research Maatschappij B.V. Catalyseur, sa préparation et son utilisation
US20100022816A1 (en) * 2008-07-22 2010-01-28 Fina Technology, Inc. Dehydrogenation of Methylbutenes to Isoprene
CN101804350A (zh) * 2009-02-13 2010-08-18 北京三聚环保新材料股份有限公司 一种载体用氧化铁的制备方法
RU2509604C1 (ru) * 2012-12-05 2014-03-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Ярославский государственный технический университет" Катализатор для дегидрирования алкилароматических углеводородов
US10316409B2 (en) * 2012-12-21 2019-06-11 Novellus Systems, Inc. Radical source design for remote plasma atomic layer deposition
US10604841B2 (en) 2016-12-14 2020-03-31 Lam Research Corporation Integrated showerhead with thermal control for delivering radical and precursor gas to a downstream chamber to enable remote plasma film deposition
WO2019113478A1 (fr) 2017-12-08 2019-06-13 Lam Research Corporation Pomme de douche intégrée à motif de trou amélioré servant à distribuer un radical et un gaz précurseur à une chambre aval en vue d'un dépôt de film de plasma à distance
EP4259729A4 (fr) * 2020-12-09 2025-01-15 DIC Corporation Particules d'oxyde de fer et procédé de production de particules d'oxyde de fer
US20250042764A1 (en) 2021-12-10 2025-02-06 Basf Se Process for the refining of iron oxides, iron oxides resulting thereof and their use
KR102632434B1 (ko) * 2022-10-14 2024-02-02 고려아연 주식회사 아연 제련 공정의 부산물인 산화철로부터 고품위 정제 산화철의 제조방법

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CN1215984C (zh) 2005-08-24
EP1379470B1 (fr) 2007-06-27
DK1379470T3 (da) 2007-10-08
DE50210381D1 (de) 2007-08-09
JP4383055B2 (ja) 2009-12-16
US20040097768A1 (en) 2004-05-20
EP1379470B2 (fr) 2012-03-14
KR20030092062A (ko) 2003-12-03
CN1501888A (zh) 2004-06-02
US7186395B2 (en) 2007-03-06
WO2002083569A3 (fr) 2002-12-12
EP1379470B9 (fr) 2012-05-02
ATE365702T1 (de) 2007-07-15
AU2002304805A1 (en) 2002-10-28
WO2002083569A2 (fr) 2002-10-24
JP2004529843A (ja) 2004-09-30

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